Production of fast dyeings



Patented May 17, 1938 UNITED STATES PATENT OFFICE PRODUCTION OF FAST DYEINGS Karl Koeberle, Heinrich Scholz, and Julius Eisele,

Ludwigshafen-on-the-Rhine, Germany,

signors to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware No Drawing. Applic'ationJune 12, 1937, Serial 11 Claims.

The present invention relates to a process of producing fast dyeings.

We have found that fibrous materials can be dyed very fast shades by applyingto the fibres acid-soluble compounds free from sulphonic groups, which are capable of coupling and which have afiinity for the fibres, in an acid bath and then allowing solutions of diazo compounds of cyclic amino compounds to act on the fibres thus treated. 1

Compounds suitable for the process are for example aza compounds of high molecular weight containing hydroxy or amino groups and also amides of cyclic hydroxycarboxylic, or of ketccarboxylic acids containing aza groups, provided the said compounds are soluble in acid and capable of coupling and have afiinity for fibres.

The dyeings are produced by first treating the fibrous materials in an acid bath, the acid content of which varies according to the nature of the compound used and may frequently be quite small, with a compound of the aforementioned kind and then treating them with a second bath containing the diazo compound. In this case also it is preferable to select compounds containing no water-solubilizing groups. In many cases it is favorable to carry out the treatment of the fibres in the presence of the usual assistants for the dyeing industry, for example with the coemployment of agents having wetting and/or dispersing action. In this way even compounds of the aforementioned kind which are soluble in acid only with comparative difficulty may be used for the process because as would be injurious to the fibres can thus be avoided.

The dyeings and prints such as may be obtained according to this invention on various materials,

as for example on wool and/or silk, leather, cotton, linen, hemp or artificial fibres, are distinguished in particular by very good fastness to moisture. By suitably selecting the initial materials it is possible to produce a great variety of shades of color. The dyeings have from good to very good fastness to light and weather and are frequently distinguished by a specially good fastness to rubbing.

Dyeings have already been produced on fibrous materials by treating the fibres with compounds capable of coupling'and then developing the dyeings by the action of aromatic diazo compounds. The compounds capable of coupling hitherto used, however, have either been insoluble in acid, in which case they have had to be applied to the fibres from alkaline baths, or they have con .ficial silk are treated for any excess of acid such In Germany July 3, 1936 having not only good general iastness but in particular also excellent uniformity. -Moreover there is the further advantage that the dyeing may be carried out simultaneously with any desired ap- 15 plication of a dyestufl or substance for improving fibres which is only, capable of use in an acid bath.

The followingexamples will further illustrate how the said invention may be carried out in practice but the invention is not restricted to 20 these examples. 1

Example 1 50 grams of a mixed fabric of wool and artiabout half an hour at 25 50 C. in a bath containing per litre 5 grams of 9-methylamino-4-azaphenanthrene and 10 cubic centimetres of per cent formic acid. The fabric thus treated is then brought into a bath containing per litre 2 grams of the diazo com 30 pound of 4-chlor-B-aminobenzotrifluoride, the dyeing being developed for about half an hour at 25 C. After hydroextraction, the fabric is rinsed with cold water and the dyeing finished off in the usual way. A clear scarlet-red dyeing of 35 excellent fastness is obtained, the uniformity and fastness to washing and rubbing being especially 3 If Q-dimethylamino 4 azaphenanthrene be used instead of 9-methyIamino-4-azaphenan- 40 threne, and diazotized 1-amino-4-nitrobenzene be used as the diazo compound, a violet dyeing is obtained.

Fast dyeings may be produced in a corresponding manner on mixed fabrics of cotton and wool 4 or fabrics of unitary fibres.

I Example 2 grams of diazotized 1-methyl-2-amino-4-chlorbenzene, the dyeing being developed for half an hour at 20 C. After rinsing, the fabric is treated for half an hour at the boiling temperature with a bath containing per litre 2 grams of a nonalkaline washing agent and 0.25 gram of sodiumhydrosulphite. A beautiful yellow dyeing is obtained which is distinguished in particular by excellent fastness to washing. rubbing, light and weather. By varying the conditions during the bottoming or developing, it is possible, for example in the case of mixed fabrics, to effect a more or less strong dyeing of the wool as compared with the other fibres. For example the temperature of one of the baths or the amount of acid in the bottoming bath may be increased.

compounds,

Instead of acetoacetyl-9-amino-4-azaphenanthrene, there may also be used hydroxycarboxylic acid amides of aza compounds. By development with diazo compounds, dyeings are thus obtained having a great variety of shades of color.

Example 3 50 grams of a fabric of cotton and/or wool and/or artificial silk are treated for half an hour at 50 C. in a bath containing per litre 4 grams of aminohydroxy-i-azaphenanthrene (obtained by treating 1.3-dihydroxy-i-azaphenanthrene with aqueous ammonia under pressure) 'and 10 cubic centimetres of 85 per cent formic acid. The fabric thus treated is introduced into a bath containing per litre 2 grams of diazotized 1- amino-3-methyl-4-cyano-6-chlorbenzene, t h e dyeing being developed for half an hour at 30 C. After hydroextraction, the fabric is rinsed with cold water and the dyeing finished off in the usual manner. It is golden-yellow and very fast to washing, rubbing and light.

Dyeings having a great variety of shades are obtained by using, instead of the diazo compounds specified in Examples 1 to 3, other diazo as for example of 1-amino-2.5-dichlorbenzene, l-amino-2-methoxy-5-benzyl-sulphone-benzene, 3-amino-4-methoxy-1-ethyl-su.l-

phone-benzene, 1-nitro-2-amino-benzene, 1- methyl-2-amino-5-chlorbenzene,' 1 methyl 2 amino-B-nitrobenzene, l-amino-3-chlorbenzeiie, 2-amino-diphenyl-sulphone, 1-methyl-3-nitro-4- aminobenzene, 1-trifiuormethyl-3-aminophenyl- 4-ethyl-sulphone, 1-amino-2-trifiuormetlrvl-4- chlorbenzene, 4 amino-4-methoxy diphenylamine, 4-amino-diphenylamine, 1-methoxy-2- amino-5-nitrobenzene, aminobenzene, 1-amino-4-benzoylamino-2.5-dimethoxy-benzene, 3-methoxy-4-ammodiphenylgeommises treating amine, 4.4-diamino-3.3-dimethoiwdiphenyl, 1-

amino-4-benzoylamino-2.5-diethoxybenzene and l-methyl-3-amino 4 -methoxy -6 benzoylaminobenzene. 7

Example 4 50 grams of a mixed-fabric of '75 per cent wool and 25 per cent staple fibre (Zellwolle) are treated in a bath containing per litre 6' grams of 2'.3-hydroxynaphthoyl 2-amino-pyridipe 1 a n d 150 cubic centimetres of per cent siilphuric acid for half an hour at 50 C. The fabricfthus treated is then introduced into a bath contain-- Y of 3 grams of 4.4'-dichlor-2-aminodiphenylether. ,The dyeing is developed at between 40 and 50 C. during 30 minutes; and the fabric is rinsed and treated for half an hour at boiling temperature in a bath containing per litre 2 grams of a non-alkaline washing agent. The fabric is dyed a strong red shade having good fastness properties.

The fabric thus diazo compounds to act on the fibres Example 5 50 grams of a mixed fabric of 75 per cent wool and 25 per cent staple fibre (Zellwofle) are treated in a bath which contains per litre 6 grams of 1-quinolyl-3-methyl-5.-pyrazolone (obtainable by reacting 8-hydraz'inoquinoline with acetic acid ester) and 24 cubic centimetres of 30 per cent acetic acid, at 50 C. for half an hour. treated is then introduced into a bath containing per litre the diazo compound of 3 grams of 1-methyl-2-amino-4-chlorbenzene, the dyeing being developed for 30 minutes at between and 30 C., and treated in a bath for 30 minutes at the boiling temperature which bath contains per litre 2 grams of a non-alkaline washing agent. The fabric is dyed an intense reddishyellow shade. The wool and the staple fibre are uniformly coyered.

What we claim iszl. A process of producing fast dyeings which comprises treating in an acid bath the material to be dyed with aza compounds free from sulphonic'groups which have affinity for the said material and are capable of coupling, and then allowing solutions of diazo compounds to act on the fibres thus treated.

2. A process of producing fast dyeings which comprises treating in an acid bath the material to be dyed with aza compounds free from sulphonic groups having at least three rings which have afiinity for the said material and are capable of coupling, and then allowing solutions of thus treat- 3. A process of producing fast dyeings which comprises treating in an acid bath the material to be dyed with aminoazaphenanthrenes free from sulphonic groups which have affinity for the said material and arecapable of coupling, and then allowing solutions of diazo compounds to act on the fibres thus treated.

- 4. A process of producing fast dyeings which comprises treating in an acid bath the material to be dyed with Q-aminoazaplienanthrene and then allowing solutions of diazo compounds to act/ "on the fibres thus treated.

5. A process of producing fast dyeings-which comprises treating in an acid bath the material to be dyed with acylaminoazaphenanthrenes free from sulphonic' groups which have ailinity for the said material and are capable of coupling, and then allowing solutions of diazo compounds 1 methoxy 3 .to act on the fibres thus treated.

6.- A process of producing fast dyeings which in an acid bath the material to be dyed with ac laminoazaphenanthrenes the acyl group of which is that of an enolizable keto carboxylic acid, and then allowing solutions of diazo compounds to act on the fibres thus treated. Y

'I. A process of producing fast dyeings which comprises treating in an acid bath the material to be dyed with acetoacetylaminoazaphenana threnes, and then allowing solutions of diazo compounds to act on the fibres thus treated.

8. A process of producing fast dyeings which comprises treating in an acid bath the material to be'dyed with 9-acetoacetylaminoazaphenanthrene, and then allowing solutions of diazo compounds to act on the fibres thus treated.

9. A process of producing fast dyeings which comprises treating in an acid bath the material to'be dyed with amides of cyclic hydroxy carboifylic acids capable of coupling having at least one aza group in the molecule, and than allowing solutions of diazo compounds to act on the fibres thus treated.

10. A process of producing fast dyeings which comprises treating in an acid bath the material to be dyed with amides of aromatic ortho-hydroxy carboxylic acids capable of coupling having at least one aza group in the molecule, and then allowing solutions of diazo compounds to act on the fibres thus treated.

11. A process of producing fast dyeings which 3-carboxylic acid containing in the amido group I the radical of an aza compound, and then allow- KARL KOEBERLE. HEINRICH SCHOLZ. JULIUS EISELE.

comprises treating in an acid bath the material to be dyed with amides of 2-hydroxynaphthalene- 

